PSG has now secured the season-opening cup on 14 separate times.
The Parisian giants needed a stoppage-time leveler followed by a successful spot-kick decider to overcome their arch-rivals in the Gulf and capture a fourth straight French Super Cup title.
The European champions seemed to be sailing towards a straightforward triumph in the showdown featuring the French league winners and the French Cup holders after the French winger found the scoring early on.
However, Marseille fired two times late to seize a shock advantage. First, the English forward scored from the spot-kick, before the defender inadvertently turned the ball into his own net for an own goal.
In a breathtaking twist of events, Goncalo Ramos snatched a vital equaliser in the final seconds to send the contest into a penalty shootout. PSG goalkeeper Chevalier then emerged as the key figure, saving decisive attempts from O'Riley and Hamed Traore.
From the spot, Ramos, the midfielder, Nuno Mendes, and Desire Doue all scored with composure for Paris Saint-Germain to seal a 4-1 shootout win.
Now 14-time winners Paris Saint-Germain, who met last season's Ligue 1 second-placed team Olympique de Marseille after completing a league and cup double, have now lifted this competition for the twelfth time in the last 13 seasons.
